Transition from a Metal‐Localized Mixed‐Valence Compound to a Fully Delocalized and Bridge‐Biased Electrophore in a Ruthenium–Amine–Ruthenium Tricenter System |
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| Authors: | Jian‐Hong Tang Dr. Jiang‐Yang Shao Yan‐Qin He Dr. Si‐Hai Wu Prof. Jiannian Yao Prof. Yu‐Wu Zhong |
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| Affiliation: | 1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, P. R. China;2. University of Chinese Academy of Sciences, Beijing, P.R. China |
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| Abstract: | A series of cyclometalated diruthenium complexes with a redox‐active amine bridge were synthesized. Depending on the terminal ligands of the ruthenium components and the substituent on the amine unit, the one‐electron‐oxidized state can be either in the form of a weakly or strongly coupled mixed‐valence diruthenium complex, a fully charge‐delocalized three‐center system, or a bridge‐biased electrophore. This transition among different electronic forms was supported by electrochemistry, near‐infrared absorption, electron paramagnetic resonance, and density functional theory analysis. |
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| Keywords: | density functional calculations electrochemistry electron transfer mixed-valence compounds ruthenium |
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